• Economic and Environmental Geology
• /
• v.46 no.3
• /
• pp.221-234
• /
• 2013

Laboratory experiments for the reaction with supercritical $CO_2$ under the $CO_2$ sequestration condition were performed to investigate the mineralogical and geochemical weathering process of the sandstones and mudstones in the Pohang basin. To simulate the supercritical $CO_2$-rock-groundwater reaction, rock samples used in the experiment were pulverized and the high pressurized cell (200 ml of capacity) was filled with 100 ml of groundwater and 30 g of powdered rock samples. The void space of the high pressurized cell was saturated with the supercritical $CO_2$ and maintained at 100 bar and $50^{\circ}C$ for 60 days. The changes of mineralogical and geochemical properties of rocks were measured by using XRD (X-Ray Diffractometer) and BET (Brunauer-Emmett-Teller). Concentrations of dissolved cations in groundwater were also measured for 60 days of the supercritical $CO_2$-rock-groundwater reaction. Results of XRD analyses indicated that the proportion of plagioclase and K-feldspar in the sandstone decreased and the proportion of illite, pyrite and smectite increased during the reaction. In the case of mudstone, the proportion of illite and kaolinite and cabonate-fluorapatite increased during the reaction. Concentration of $Ca^{2+}$ and $Na^+$ dissolved in groundwater increased during the reaction, suggesting that calcite and feldspars of the sandstone and mudstone would be significantly dissolved when it contacts with supercritical $CO_2$ and groundwater at $CO_2$ sequestration sites in Pohang basin. The average specific surface area of sandstone and mudstone using BET analysis increased from $27.3m^2/g$ and $19.6m^2/g$ to $28.6m^2/g$ and $26.6m^2/g$, respectively, and the average size of micro scale void spaces for the sandstone and mudstone decreased over 60 days reaction, resulting in the increase of micro pore spaces of rocks by the dissolution. Results suggested that the injection of supercritical $CO_2$ in Pohang basin would affect the physical property change of rocks and also $CO_2$ storage capacity in Pohang basin.

• The Journal of Engineering Geology
• /
• v.21 no.2
• /
• pp.163-178
• /
• 2011

A test borehole was drilled in the Cheongwon area to investigate the relationship between geochemical environment and the natural occurrence of radioactive materials (uranium and Rn-222) in borehole groundwater. The borehole encountered mainly biotite schist and biotite granite, with minor porphyritic granite and basic dykes. Six groundwater samples were collected at different depths in the borehole using the double-packed system. The groundwater pH ranges from 5.66 to 8.34, and the chemical type of the groundwater is Ca-$HCO_3$. The contents of uranium and Rn-222 in the groundwater are 0.03-683 ppb and 1,290-7,600 pCi/L, respectively. The contents of uranium and thorium in the rocks within the borehole are 0.51-23.4 ppm and 0.89-62.6 ppm, respectively. Microscope observations of the rock core and analyses by electron probe microanalyzer (EPMA) show that most of the radioactive elements occur in the biotite schist, within accessory minerals such as monazite and limenite in biotite, and in feldspar and quartz. The high uranium content of groundwater at depths of -50 to -70 m is due to groundwater chemistry (weakly alkaline pH, an oxidizing environment, and high concentrations of bicarbonate). The origin of Rn-222 could be determined by analyzing noble gas isotopes (e.g., $^3He/^4He$ and $^4He/^{20}Ne$).

• Korean Journal of Mineralogy and Petrology
• /
• v.35 no.3
• /
• pp.313-331
• /
• 2022

Natural or native abiotic molecular hydrogen (H₂) is a major component in natural gas, however yet its importance in the global energy sector's usage as clean and renewable energy is underestimated. Here we review the occurrence and geological settings of native hydrogen to demonstrate the much widesprease H₂ occurrence in nature by comparison with previous estimations. Three main types of source rocks have been identified: (1) ultramafic rocks; (2) cratons comprising iron (Fe²⁺)-rich rocks; and (3) uranium-rich rocks. The rocks are closely associated with Precambrian crystalline basement and serpentinized ultramafic rocks from ophiolite and peridotite either at mid-ocean ridges or within continental margin(Zgonnik, 2020). Inorganic geological processes producing H₂ in the source rocks include (a) the reduction of water during the oxidation of Fe²⁺ in minerals (e.g., olivine), (b) water splitting due to radioactive decay, (c) degassing of magma at low pressure, and (d) the reaction of water with surface radicals during mechanical breaking (e.g., fault) of silicate rocks. Native hydrogen are found as a free gas (51%), fluid inclusions in various rock types (29%), and dissolved gas in underground water (20%) (Zgonnik, 2020). Although research on H₂ has not yet been carried out in Korea, the potential H₂ reservoirs in the Gyeongsang Basin are highly probable based on geological and geochemical characteristics including occurrence of ultramafic rocks, inter-bedded basaltic layers and iron-copper deposits within thick sedimentary basin and igneous activities at an active continental margin during the Permian-Paleogene. The native hydrogen is expected to be clean and renewable energy source in the near future. Therefore it is clear that the origin and exploration of the native hydrogen, not yet been revealed by an integrated studies of rock-fluid interaction studies, are a field of special interest, regardless of the presence of economic native hydrogen reservoirs in Korea.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
• /
• v.11 no.2
• /
• pp.95-102
• /
• 2013

There was a study for biological characteristics, except for physico-chemical and mineralogical properties, on the natural bentonite that is considered as a buffer material for the high-level radioactive waste disposal site. A bentonite slurry that was prepared from a local 'Gyeongju bentonite' in Korea was incubated in a serum bottle with nutrient media over 1 week and its stepwise change was observed with time. From the activated bentonite in the nutrient media, we can find a certain change of both solid and liquid phases. Some dark and fine sulfides began to be generated from dissolved sulfate solution, and 4 species of sulfate-reducing bacteria (SRB) were identified as living cells in samples that were periodically taken and incubated. These results show that sulfate-reducing (or metal-reducing) bacteria are adhering and existing in the powder of bentonite, suggesting that there may be a potential occurrence of longterm biogeochemical effects in and around the bentonite buffer in underground anoxic environmental conditions.

• The Journal of Engineering Geology
• /
• v.18 no.1
• /
• pp.103-115
• /
• 2008

The purposes of this study are to understand characteristic water-rock interaction mechanisms of groundwater in the granite area of Geochang and Hapcheon areas, Gyeongnam-do and to clarify the origin of fluoride. The possible water-rock interaction process and the source of fluorine were studied using water chemistry, rock chemistry, mineralogy by XRD, and microtexture analysis by backscattered electron image of the electron microprobe. No clear relationships between F and hardness was found. But the fluorine content increases to some extent with pH and well depth. Preferential alteration due to water-rock interaction took place along edges or cleavage, or margins of biotite. Because biotite is highly subject to alteration in granite aquifer, fluorine in groundwater is originated from the leaching of biotite.

• Proceedings of the KSRS Conference
• /
• 2007.03a
• /
• pp.210-215
• /
• 2007

북극 다산기지가 있는 니알슨 인근 해역인 Kongsfjorden만은 일부 해역이 해빙으로 덮혀 있는 반폐쇄적인 만으로 수심이 평균 200m 이상 된다. 이곳 북극 지방은 하절기 라도 태양의 고도가 낮아 해색위성분야의 극지활용에 대한 가능성 여부도 명확하게 알려져 있지 못하다. 따라서 본 연구에서는 북극 다산기지가 위치한 스발바드 군도의 니알슨 주변 해역(Kongsfjorden 해역)을 중심으로 2006년 8월 현장관측된 자료들을 유사한 시기의 한반도 주변 해역에서 현장관측된 자료들과 비교/분석하여 해양환경적 특성과 해수광학적인 특성이 어떤 차이가 있는지를 비교 분석하였다. 또한 북극 지방에서 인공위성을 이용한 해색위성자료의 극지활용이 가능한지를 검토하였다. 해수의 광 특성으로, 니알슨 주변 해역의 ${\alpha}^*_{ph}(440)$ 최대값은 $0.1m^2/mg$으로 한반도 주변해수의 ${\alpha}^*_{ph}(440)$ 최대값보다 약 2배정도 높게 측정되어 플랑크톤의 광 흡수효율이 중위도보다 상대적으로 높은 것으로 분석되었다. ${\alpha}^*_{ss}(440)$ 값은 $0.04-0.1m^2/g$으로 동중국해와 유사하며，한반도 주변해수보다 높은 값을 나타냈다. 이것은 Kongsfjorden 해역의 부유물질(SS) 구성성분이 동중국해와 유사한 무기광물 입자로 주로 구성되어 있음을 보여주고 있다. ${\alpha}_{dom}(400)$ 값은 $0.08-0.25m^{-1}$로 한반도 주변해수의 ${\alpha}_{dom}(400)$이 값과 유사하고 연안해역의 ${\alpha}_{dom}(400)$ 값보다 낮은 값을 나타냈다. $E_d(460)$의 평균값은 Konsfjorden 해역 $40mW/cm^2/{\mu}m$, 동중국해 $120mW/cm^2/{\mu}m$, 황해남부 $110mW/cm^2/{\mu}m$, 남해연안 $100mW/cm^2/{\mu}m$, 진해만 $100mW/cm^2/{\mu}m$이었다. 이와 같은 현장관측결과를 토대로 분석한 북극 다산기지 주변 해역의 해수광학적인 환경 특성은 용존유기물의 흡광도를 기준으로 볼 때 대양(Open Sea)의 광 특성과 유사하였다. 또한 북극지방에서 태양의 해수 입사 광량은 중위도의 약 40%정도이지만 해색위성자료의 극지활용이 가능하다고 판단되었다.

• Journal of the Korean Society of Groundwater Environment
• /
• v.5 no.4
• /
• pp.177-191
• /
• 1998

For various kinds of waters including surface water, shallow groundwater (＜70 m deep) and deep groundwater (500∼810 m deep) from the Pungki area, an integrated study based on hydrochemical, multivariate statistical, thermodynamic, environmental isotopic (tritium, oxygen-hydrogen, carbon and sulfur), and mass-balance approaches was attempted to elucidate the hydrogeochemical and hydrologic characteristics of the groundwater system in the gneiss area. Shallow groundwaters are typified as the 'Ca-HCO$_3$'type with higher concentrations of Ca, Mg, SO$_4$and NO$_3$, whereas deep groundwaters are the 'Na-HCO$_3$'type with elevated concentrations of Na, Ba, Li, H$_2$S, F and Cl and are supersaturated with respect to calcite. The waters in the area are largely classified into two groups: 1) surface waters and most of shallow groundwaters, and 2) deep groundwaters and one sample of shallow groundwater. Seasonal compositional variations are recognized for the former. Multivariate statistical analysis indicates that three factors may explain about 86% of the compositional variations observed in deep groundwaters. These are: 1) plagioclase dissolution and calcite precipitation, 2) sulfate reduction, and 3) acid hydrolysis of hydroxyl-bearing minerals(mainly mica). By combining with results of thermodynamic calculation, four appropriate models of water/ rock interaction, each showing the dissolution of plagioclase, kaolinite and micas and the precipitation of calcite, illite, laumontite, chlorite and smectite, are proposed by mass balance modelling in order to explain the water quality of deep groundwaters. Oxygen-hydrogen isotope data indicate that deep groundwaters were originated from a local meteoric water recharged from distant, topograpically high mountainous region and underwent larger degrees of water/rock interaction during the regional deep circulation, whereas the shallow groundwaters were recharged from nearby, topograpically low region. Tritium data show that the recharge time was the pre-thermonuclear age for deep groundwaters (＜0.2 TU) but the post-thermonuclear age for shallow groundwaters (5.66∼7.79 TU). The $\delta$$\^$34/S values of dissolved sulfate indicate that high amounts of dissolved H$_2$S (up to 3.9 mg/1), a characteristic of deep groundwaters in this area, might be derived from the reduction of sulfate. The $\delta$$\^$13/C values of dissolved carbonates are controlled by not only the dissolution of carbonate minerals by dissolved soil CO$_2$(for shallow groundwaters) but also the reprecipitation of calcite (for deep groundwaters). An integrated model of the origin, flow and chemical evolution for the groundwaters in this area is proposed in this study.

• Economic and Environmental Geology
• /
• v.36 no.4
• /
• pp.285-293
• /
• 2003

Tailings of Dukum mine in the vadose and saturated zone were investigated to reveal the mobility of metal elements and the condition of mineralogical solubility according to redox environments throughout the geochemical analysis, thermodynamic modelling, and mineralogical study for solid-samples and water samples(vadose zone; distilled water: tailings=5 : 1 reacted, saturated zone; pore-water extracted). In the vadose zone, sulfide oxidation has generated low-pH(2.72∼6.91) condition and high concentration levels of S $O_4$$^{2-}$(561∼1430mg/L) and other metals(Zn : 0.12∼l57 mg/L, Pb : 0.06∼0.83 mg/L, Cd : 0.06∼l.35 mg/L). Jarosite$(KFe_3(SO_4)_2(OH)_6)$ and gypsum$(CaSO_4{\cdot}2H_2O$) were identified on XRD patterns and thermodynamics modelling. In the saturated zone, concentration of metal ions decreased because pH values were neutral(7.25∼8.10). But Fe and Mn susceptible to redox potential increased by low-pe values(7.40∼3.40) as the depth increased. Rhodochrosite$(MnCO_3)$ identified by XRD and thermodynamics modelling suggested that $Mn^{4+}$ or $Mn^{3+}$ was reduced to $Mn^{2+}$. Along pH conditions, concentrations of dissolved metal ions has been most abundant in vadose zone throughout borehole samples. It was observed that pH had more effect on metal solubilities than redox potential. How-ever, the release of co-precipitated heavy metals following the dissolution of Fe-Mn oxyhydroxides could be the mechanism by which reduced condition affected heavy metal solubility considering the decrease of pe as depth increased in tile saturated zone.

• Economic and Environmental Geology
• /
• v.55 no.4
• /
• pp.377-388
• /
• 2022

Laboratory-scale experiments were performed to identify the As removal mechanism of the residual slag generated after the mineral carbonation process. The residual slags were manufactured from the steelmaking slag (blast oxygen furnace slag: BOF) through direct and indirect carbonation process. RDBOF (residual BOF after the direct carbonation) and RIBOF (residual BOF after the indirect carbonation) showed different physicochemical-structural characteristics compared with raw BOF such as chemical-mineralogical properties, the pH level of leachate and forming micropores on the surface of the slag. In batch experiment, 0.1 g of residual slag was added to 10 mL of As-solution (initial concentration: 203.6 mg/L) titrated at various pH levels. The RDBOF showed 99.3% of As removal efficiency at initial pH 1, while it sharply decreased with the increase of initial pH. As the initial pH of solution decreased, the dissolution of carbonate minerals covering the surface was accelerated, increasing the exposed area of Fe-oxide and promoting the adsorption of As-oxyanions on the RDBOF surface. Whereas, the As removal efficiency of RIBOF increased with the increase of initial pH levels, and it reached up to 70% at initial pH 10. Considering the PZC (point of zero charge) of the RIBOF (pH 4.5), it was hardly expected that the electrical adsorption of As-oxyanion on surface of the RIBOF at initial pH of 4-10. Nevertheless it was observed that As-oxyanion was linked to the Fe-oxide on the RIBOF surface by the cation bridge effect of divalent cations such as Ca²⁺, Mn²⁺, and Fe²⁺. The surface of RIBOF became stronger negatively charged, the cation bridge effect was more strictly enforced, and more As can be fixed on the RIBOF surface. However, the Ca-products start to precipitate on the surface at pH 10-11 or higher and they even prevent the surface adsorption of As-oxyanion by Fe-oxide. The TCLP test was performed to evaluate the stability of As fixed on the surface of the residual slag after the batch experiment. Results supported that RDBOF and RIBOF firmly fixed As over the wide pH levels, by considering their As desorption rate of less than 2%. From the results of this study, it was proved that both residual slags can be used as an eco-friendly and low-cost As remover with high As removal efficiency and high stability and they also overcome the pH increase in solution, which is the disadvantage of existing steelmaking slag as an As remover.

• The Journal of Engineering Geology
• /
• v.23 no.2
• /
• pp.171-186
• /
• 2013

A drilling project was undertaken to characterize the geochemical relationship and the occurrence of radioactive materials at a test site among public-use groundwaters previously known to have high occurrence of uranium and radon-222 in the Daejeon area. A borehole (121 m deep) was drilled and core rocks mainly consist of two-mica granite, and associated with pegmatite and dykes of intermediate composition. The groundwater samples collected at six different depths in the borehole by a double-packed system showed the pH values ranging from neutral to alkaline (7.10-9.3), and electrical conductivity ranging from 263 to 443 ${\mu}S/cm$. The chemical composition of the borehole groundwaters was of the $Ca-HCO_3(SO_4+Cl)$ type. The uranium and Rn-222 contents in the groundwater were 109-1,020 ppb and 9,190-32,800 pCi/L, respectively. These levels exceed the regulation guidelines of US EPA. The zone of the highest groundwater uranium content occurred at depths of 45 to 55m. The groundwater chemistry in this zone (alkaline, oxidated, and high in bicarbonate) is favorable for the dissolution of uranium into groundwater. The dominant uranium complex in groundwater is likely to be $(UO_2CO_3)^0$ or $(UO_2HCO_3)^+$. Radon-222 content in groundwater shows an increasing trend with depth. The uranium and thorium contents in the core were 0.372-47.42 ppm and 0.388-11.22 ppm, respectively. These levels are higher values than those previously been reported in Korea. Microscopic observations and electron microprobe analysis(EPMA) revealed that the minerals containing U and Th are monazite, apatite, epidote, and feldspar. U and Th in these minerals are likely to substitute for major elements in crystal lattice.